Process for the production of broken-down organic lignin-cellulose silicate polymers

ABSTRACT

Small particles of cellulose-containing plants are mixed with an alkali metal hydroxide and an oxidated silicon compound, then heated to 150° C. to 220° C. while agitating, thereby producing a broken-down lignin-cellulose silicate polymer which is then reacted with a substituted organic compound to produce an organic broken-down lignin-cellulose silicate polymer and may be used as molding powder and as a coating agent.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application, Ser. No.257,126, filed on Apr. 24, 1981, now U.S. Pat. No. 4,313,857 which is adivision of my copending U.S. patent application Ser. No. 203,730, filedNov. 3, 1980 pending, which is a continuation-in-part of my copendingU.S. patent application, Ser. No. 112,290 filed Jan. 15, 1980 now Pat.No. 4,220,757, which is a continuation-in-part of my U.S. patentapplication, Ser. No. 29,202 filed Apr. 12, 1979, now U.S. Pat. No.4,220,757.

BACKGROUND OF THE INVENTION

This invention relates to a process for the production of an organicbroken-down lignin-cellulose silicate polymer utilizing a water-solublebroken-down cellulose silicate polymer and a substituted organiccompound in an aqueous solution which are reacted to produce an organicbroken-down lignin-cellulose silicate polymer which may be in the formof a fine precipitated or as an aqueous dispersion.

The products produced by this invention have many commerical uses andmay be utilized as molding powder, as coating agents for wood and metal,as films, as fillers, as impregnating agents, as adhesives, as binders,as caulking material, as fibers, as sheets, as casting materials, asputty material and may be further reacted with organic compounds toproduce useful resinous products and foams.

An organic broken-down lignin-cellulose silicate polymer is obtained byreacting the following components:

Component (a): Broken-down alkali metal lignin-cellulose silicatepolymer;

Component (b): An organic compound having a substituent which will splitoff during the reaction;

Component (c): Optionally, a solvent;

Component (d): Optionally, an emulsifying or dispersion agent.

Component (a)

Component (a) a broken-down alkali metal lignin-cellulose silicateproduct, is produced by the processes outlined in my U.S. patentapplication, Ser. No. 629,202, filed Apr. 12, 1979, now U.S. Pat. No.4,220,757, and is incorporated into this invention.

Water-soluble, broken-down, alkali metal lignin-cellulose silicatepolymers and carbohydrates are produced by mixing 3 parts by weight of acellulose-containing plant or plant derivatives, 1 to 2 parts by weightof an oxidated silicon compound, and 2 to 5 parts by weight of an alkalimetal hydroxide, then heating the mixture at 150° C. to 220° C. whileagitating for 5 to 60 minutes.

Any suitable plant or the products of plants which contain cellulose maybe used in this invention. The plant material is preferred to be in theform of small dry particles such as sawdust. Suitable plants include,but are not limited to, trees, bushes, agricultural plants, weeds,vines, straw, flowers, kelp, algae and mixtures thereof. Wood is thepreferred plant. Commercial and agricultural waste products may be used,such as stalks, paper, cotton clothes, bagasses etc. Wood fibers (woodpulp) with lignin removed may be used in this invention. Plants thathave been partially decomposed, such as humus, peat, certain soft browncoal, manure containing cellulose, etc., may also be used in thisinvention.

Any suitable oxidated silicon compound may be used in this invention.Suitable oxidated silicon compounds include silica, e.g., hydratedsilica, hydrated silica containing Si-H bonds (silicoformic acid),silica sol, silicic acid, silica, etc.; alkali metal silicates, e.g.,sodium silicate, potassium silicate, lithium silicate, etc., naturalsilicates with free silicic acid groups and mixtures thereof.

Silica sol is the preferred oxidated silicon compound.

Any suitable alkali metal hydroxide may be used in this invention.Suitable alkali metal hydroxides include sodium hydroxide, potassiumhydroxide and mixtures thereof. Sodium hydroxide is the preferred alkalimetal hydroxide.

The novel broken-down water-soluble alkali metal lignin cellulosesilicate polymer produced by the process of this invention differs fromthe alkali cellulose silicate polymers produced by the known processes.The broken-down alkali metal lignin-cellulose silicate polymer is darkbrown to black in color, has at least one -COH radical removed from eachcellulose molecule, the usual lignin-cellulose bond is not broken inmost of the cases and the cellulose molecules are broken down intosmaller molecules of alkali metal broken-down lignin-cellulose silicatewhich are water-soluble. When a cellulose polymer such as cotton or woodwith the lignin removed is reacted with an alkali metal hydroxide by theprocess of this invention, and an oxidated silicon compound, a blackwater-soluble broken-down alkali metal cellulose polymer is produced;this polymer may be reacted with a mineral acid until the pH is about 6and a black, foamed, broken-down cellulose silicate resinous product andcarbohydrates are produced. The foam is produced by the release of CO₂which was removed from the cellulose polymer. When a mineral acid isadded to an aqueous solution of the broken-down alkali metallignin-cellulose silicate polymer until the pH is about 6, a blackresinous product floats to the top or is precipitated and is recoveredand the carbohydrates are in the solution.

Component (b)

Any suitable organic compound that will react with the broken-downalkali metal lignin-cellulose silicate polymer may be used. An organiccompound is preferred, having a substitutent, which splits off duringthe reaction. These organic compounds which are the reactants used inthe preparation of broken-down organic lignin-cellulose silicatepolymers have the graphical skeleton carbon structure of: ##STR1##

where X represents the substituents which split off during the reaction.The R, R' and R" are selected from the following groups: hydrogen,saturated straight-chain carbon atoms, unsaturated carbon atoms, etherlinkages, aromatic structures, another X and others, for it is to beunderstood that other structures may be employed. The X substituents canbe halogen, acid sulfate, nitrate, acid phosphate, bicarbonate, sulfateformate, acetate, propionate, laurate, oleate, stearate, acid oxalate,acid malonate, acid tartrate, acid citrate, mixtures thereof and others.

Suitable substituted organic compounds include, but are not limited to,substituted alkyl compounds such as methyl halides such as methylchloride, methyl bromide, methyl iodide, etc., methyl sulfate, methylhydrogen, sulfate, methyl hydrogen phosphate, methyl nitrate; ethylhalides such as ethyl chloride, ethyl bromide, ethyl iodide, etc., ethylhydrogen sulfate, ethyl sulfate, ethyl hydrogen phosphate, ethylnitrate, ethyl oxalate; propyl halides, propyl hydrogen sulfate,1-nitropropane, 2-nitropropane, propyl hydrogen phosphate; butylhalides, butyl hydrogen sulfate, 2-nitro-1-butanol, butyl hydrogenphosphate, etc.,; substituted unsaturated compounds such as vinylchloride, vinyl bromide, vinyl acetate, vinylidine chloride; substitutedcarboxyic acids such as chloroacetic acid, dichloroacetic acid, sodiumchloroacetate, bromoacetic acid, iodoacetic acid, α-chloropropionicacid, α-chlorobutyric acid, etc.; acid chlorides such as acetylchloride, acetyl bromide, propionyl chloride, n-butyryl chloride,chloroacetic chloride, etc.; substituted allyl halides such as allylhalide, methyl allyl halide, etc.; carboxyl acid anhydrides such asacetic anhydride, propionic anhydride, n-butyric anhydride, isobutyricanhydride, etc.; organic esters such as ethyl acetate, methylpropionate, propyl formate, methyl formate, ethyl formate, methylacetate, n-butyl acetate, ethyl chloroacetate, etc.; substitutedhydroxyl compounds such as alkene halohydrins such as ethylenechlorohydrin, dthylene bromohydrin, glyceryl monochlorohydrin, etc.;substituted benzene compounds such as benzyl chloride, benzal chloride,nitrobenzene and p-chlorobenzoic acid.

Component (c)

Any suitable inorganic or organic solvent may be used in this invention.Suitable solvents include, but are not limited, to, water, alcohols,such as methyl alcohol, ethyl alcohol, isopropyl alcohol, propylalcohol, polyhydroxy organic compounds (polyol) such as ethylene glycol,propylene-1,2 and -2,3-glycol, butylene-1,4- and -2,3-glycol,hexane-1,6-diol, 2-methyl-propane-1,3-diol, glycerol, trimethylolpropane, hexane-1,2,6-triol, butane-1,2,4-triol, trimethylol ethane,pentaerythritol, diethylene glycol, triethylene glycol, tetraethyleneglycol, polyethylene glycol, dipropylene glycol, polypropylene glycol,dilintylene glycol, polybutylene glycols; polyesters, polyethers,sucrose polyethers and sucrose amine polyethers with at least 2,generally from 2 to 8, hydroxyl groups per molecule, and mixturesthereof.

Component (d)

Emulsifying or dispersing agents may be used in this invention, anysalt-stable compound which is highly hydrophobous in nature and has ahydrophobic group as one component and a hydrophilic group as the othermay be used. The emulsifying or dispersing agent which may be used forthe formation of lattices of small-particle size are those compoundshaving such groups as SO₃, SO₄, NE₂, etc., as the hydrophilic componentand a higher molecular weight alkyl, aralkyl, aryl or alkyl group as thehydrophobic component. The more hydrophobic the entire compound becomes,the smaller the polymer particle size becomes in the latex.

Compounds which are most suitable as emulsifying or dispersing agentsfor latex formation are the lignin sulfonates such as calcium and sodiumlignin sulfonates, alkyl benzene sulfonates having more than 20 carbonatoms in the alkyl groups, aryl alkyl sulfonates, sorbitan monolaurates,especially those which are oil-soluble, and others. The dominance of thehydrophobic group over the hydrophilic groups is one of the importantfactors in producing a latex of small-particle size. The molecularweight of the hydrophobic group alone is not the deciding factor, foraryl groups, for example, may be more hydrophobic than an alkyl grop oflike molecular weight. Aryl alkyl groups are more hydrophobic than alkylaryl groups of the same molecular weight. Thus, by selection ofemulsifying or dispersing agents, the particle size of the latex can bevaried to suit any particle needs. Emulsifiers which can be used aresorbitan monolaurates, alkyl aryl sulfonates, alkyl aryl sulfates, arylalkyl sulfonates, aryl alkyl sulfates, lignin sulfonates, methylcellulose, sulfonated petroleum fractions, polymerized alkyl arylsulfonates, polymerized aryl alkyl sulfonates, soybean lecithin,silicone surfactants and the like. The particle size can be controlledby selecting emulfisying or dispersing agents having differentmolecular-weight hydrophobic groups as well as different hydrophobicgroups. The particle size will also vary with the concentration of theemulsifying or dispersing agents.

Epihalohydrin may be added with the substituted organic compound up toan amount by weight equal to the weight of the substituted organiccompound and selected from the group consisting of epichlorohydrin,epibromohydrin, methyl epichlorohydrin, di-epi-iodohydrin,eipfluorohydrin, epiiodohydrin and mixtures thereof. Epichlorohydrin isthe preferred epihalohydrin.

Organic oxides may be used in this invention, such as ethylene oxide,propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran andmixtures thereof up to an amount by weight equal to the weight of thesubstituted organic compound.

The primary object of this invention is to produce organic broken-downlignin-cellulose silicate polymers. Another object is to produce organicbroken-down lignin-cellulose silicate polymer that may be used asmolding powder, as coating agents for wood and metal, as films, asfilters, as impregnating agents, as adhesives, etc. Another object is toproduce organic broken-down lignin-cellulose silicate polymers whichwill react with polyisocyanates to produce foam which may be utilized asthermal and sound insulation. Still another object is to producealdehyde broken-down organic lignin-cellulose silicate polymers.

DETAILED DESCRIPTION OF THE INVENTION

The preferred process to produce an organic broken-down lignin-cellulosesilicate polymer is to slowly add a substituted organic compoundsubstituent, which will split off during the reaction, to a broken-downmetal lignin-cellulose silicate polymer in the amount wherein the molesof the substituted radicals are about equal to the mols of the alkaliradicals in the mixture, while agitating for about 30 minutes at atemperature below the boiling temperature of the reactants; the reactionis complete in about 30 minutes to 8 hours, thereby producing an organicbroken-down lignin-cellulose silicate polymer. The salt produced may beremoved by washing with water and then filtering or by using a solvent.

In an alternate method the broken-down alkali metal lignin-cellulosesilicate polymer is added to a solvent such as water, alcohols,polyhydroxy alcohols and mixtures thereof to produce a solutioncontaining 10% to 70% broken-down alkali metal lignin-cellulose silicatepolymer, than a substituted organic compound having a substitutent whichwill split off during the reaction, is slowly added to said solutionwhile agitating at a temperature between ambient and just below theboiling temperature of the reactants and at a pressure up to 1500 psifor about 30 minutes; the reaction is complete in 30 minutes to 8 hours.When water is used as the solvent, an emulsifying or dispersing agentmay be used in the amount of 1% to 5% in order to assist in mixing thebroken-down alkali metal lignin-cellulose silicate polymer and thesubstituted organic compound. The organic broken-down lignin-cellulosesilicate polymer may be recovered by filtration from an aqueoussolution.

The chemical reaction of this invention may take place in any suitablephysical condition. Ambient pressure is usually satisfactory, but incertain conditions, an elevated or below-ambient pressure may be useful.In cases when halogenated organic compounds are used, the reaction isspeeded up by increased temperature (up to 200° C.) and pressure (up to1500 psi). When organic hydrogen sulfate compounds are used, it may benecessary to decrease the temperature by cooling the reactants. Ambienttemperature is usually satisfactory.

Any suitable aldehyde compound may be reacted with the broken-downalkali metal lignin-cellulose silicate polymer with a substitutedorganic compound or be reacted at the same time that the substitutedcompound is reacting. Suitable aldehyde include, but are not limited to,formaldehyde, acetaldehyde, propionic aldehyde, furfural,crotonaldehyde, acrolein, butyl aldehyde, paraformaldehyde pentanals,hexanals, heptanals and mixtures thereof in the ratio of 1 to 5 parts byweight of the aldehyde to 2 parts by weight of the broken-down alkalimetal lignin-cellulose polymer. The aldehyde is mixed with thewater-soluble broken-down alkali metal lignin-cellulose silicatepolymer, then agitated at a temperature between ambient temperature andthe boiling temperature of the aldehyde and at ambient pressure for 10to 20 minutes, thereby producing an aldehyde alkali metallignin-cellulose silicate polymer. The aldehyde-alkali metallignin-cellulose silicate polymer is then mixed with a substitutedorganic compound having a substituent which will split off during thereaction, to said aldehyde-alkali metal lignin-cellulose silicatepolymer in the amount wherein the mols of the substituted radicals areabout equal to the mols of the alkali radicals in the mixture, thenheated to a temperature between ambient temperature and the boilingtemperature of the reactants while agitating at an ambient pressure to1500 psi for about 30 minutes; the reaction is complete in 30 minutes to8 hours, thereby producing a broken-down organic lignin-cellulosesilicate polymer. The polymer usually gradually settles out and may berecovered by decantation or filtration.

The broken-down organic lignin-cellulose silicate polymer utilizing analdehyde may be ground into a molding powder, then molded into usefulobjects such as knobs, panels, art objects, handles, etc., by heat (180°C. to 220° C.) and by pressure. The broken-down organic lignin-cellulosesilicate polymer may be further reacted with polyisocyanates to produceuseful solid objects or foams which may be used as thermal and soundinsulation, for packaging, construction panels, etc. The organicbroken-down lignin-cellulose silicate polymer is also soluble in many ofthe common solvents and may be used as a protective coating for wood andmetal and as an adhesive.

The broken-down organic lignin-cellulose silicate polymers resinousproducts will react chemically with suitable polyisocyanates and/orpolyisothiocyanates to produce resinous products and foams. All thebroken-down organic lignin-cellulose silicate polymers contain more than2 hydroxyl and carboxyl groups per molecule.

Any suitable organic polyisocyanate may be used according to theinvention, including aliphatic, cycloaliphatic, araliphatic, aromatic,and heterocyclic polyisocyanates and mixtures thereof. Suitablepolyisocyanates which may be employed in the process of the inventionare exemplified by the organic diisocyanates which are compounds of thegeneral formula:

    O═C═N-R-N═C═O

wherein R is a divalent organic radical such as an alkylene, aralkyleneor arylene radical. Such suitable radicals may contain, for example, 2to 30 carbon atoms. Examples of such diisocyanates are:

tolylene diisocyanate,

p,p'-diphenylmethane diisocyanate,

phenylene diiocyanate,

m-xylylene diisocyanate,

chlorophenylene diisocyanate,

benzidene diisocyanate,

naphthylene diisocyanate,

decamethylene diisocyanate,

hexamethylene diisocyanate,

pentamethylene diisocyanate,

tetramethylene diisocyanate,

thiodipropyl diisocyanate,

propylene diisocyanate, and

ethylene diisocyanate.

Other polyisocyanates, polyisothiocyanates and their derivatives may beequally employed. Fatty diisocyanates are also suitable and have thegeneral formula: ##STR2## where x+y totals 6 to 22 and x is 0 to 2,e.g., isocyanastearyl isocyanate.

It is generally preferred to use commercially readily availablepolyisocyanates, e.g., tolylene-2,4- and -2,6-diisocyanate and anymixtures of these isomers ("TDI"), polyphenylpolymethylene-isocyanatesobtained by aniline-formaldehyde condensation followed by phosgenation("crude MDI"), and modified polyisocyanate containing carbodiimidegroups, allophanate groups, isocyanurate groups, urea groups, imidegroups, amide groups or bioret groups, said modified polyisocyanatesprepared by modifying organic polyisocyanates thermally or catalyticallyby air, water, urethanes, alcohols, amides, amines, carboxylic acids, orcarboxylic acid anhydrides, phosgenation products of condensates oraniline or anilines alkyl-substituted on the nucleus, or aldehydes.Ketones may be used in this invention. Solutions of distillationresidues accumulating during the production of tolylene diisocyanates,diphenyl methane diisocyanate, or hexamethylene diisocyanate, inmonomeric polyisocyanates or in organic solvents or mixtures thereof maybe used in this invention. Organic triisocyanates such astriphenylmethane triisocyanate may be used in this invention.Cycloaliphatic polyisocyanates, e.g., cyclohexylene-1,2-;cyclohexylene-1,4-; and methylene-bis-(cyclohexyl-4,4') diisocyanate maybe used in this invention. Suitable polyisocyanates which may be usedaccording to the invention are described by W. Siefkin in Justus LiebigsAnnalen der Chemie, 562, pages 75 to 136. Inorganic polyisocyanates arealso suitable according to the invention.

Organic polyhydroxyl compounds (polyols) may be used in this inventionwith polyisocyanates or may be first reacted with a polyisocyanate toproduce isocyanate-terminated polyurethane prepolymers and then alsoused in this invention.

Reaction products of from 50 to 99 mols of aromatic diisocyanates withfrom 1 to 50 mols of conventional organic compounds with a molecularweight of, generally, from about 200 to about 10,000 which contain atleast two hydrogen atoms capable of reacting with isocyanates, may alsobe used. While compounds which contain amino groups, thiol groups,carboxyl groups or silicate groups may be used, it is preferred to useorganic polyhydroxyl compounds, in particular, compounds which containfrom 2 to 8 hydroxyl groups, especially those with a molecular weight offrom about 800 to about 10,000 and, preferably, from about 1,000 toabout 6,000, e.g., polyesters, polyethers, polythioethers, polyacetals,polycarbonates or polyester amides containing at least 2, generally from2 to 8, but, preferably, dihydric alcohols, with the optional additionof trihydric alcohols, and polybasic, preferably dibasic, carboxylicacids. Instead of the free polycarboxylic acids, the correspondingpolycarboxylic acid anhydrides or corresponding polycarboxylic acidesters of lower alcohols or their mixtures may be used for preparing thepolyesters. The polycarboxylic acid may be aliphatic, cycloaliphatic,aromatic and/or heterocyclic and may be substituted, e.g., with halogenatoms and may be unsaturated. Examples include: succinic acid, adipicacid, sebacic acid, suberic acid, azelaic acid, phthalic acid, phthalicacid anhydride, isophthalic acid, tetrahydrophthalic acid anhydride,trimellitic acid, hexahydrophthalic acid anhydride, tetrachlorophthalicacid anhydride, endomethylene tetrahydrophthalic acid anhydride,glutaric acid anhydride, fumaric acid, maleic acid, maleic acidanhydride, dimeric and trimeric fatty acid such as oleic acid,optionally mixed with monomeric fatty acids, dimethylterephthalate andbis-glycol terephthalate. Any suitable polyhydric alcohols may be usedsuch as, for example, ethylene glycol, propylene-1,2- and -1,3-glycol;butylene-1,4- and -2,3-glycol; hexane-1,6-diol; octaine-1,8-diol;neopentyl glycol;cyclohexanedimethanol-(1,4-bis-hydroxymethylcyclohexane);2-methylpropane-1,3-diol; glycerol; trimethylol propane;hexane-1,2,6-triol; butane-1,2,4-triol; trimethylol ethane;pentaerythritol; quinitol; mannitol and sorbitol; methylglycoside;diethylene glycol; triethylene glycol; tetra ethylene glycol;polyethylene glycols; dipropylene glycol; polypropylene glycols;dibutylene glycol and polybutylene glycols. The polyesters may alsocontain a proportion of carboxyl end groups. Polyesters of lactones,such as c-caprolactone, or hydroxycarboxylic acid such asc-hydroxycaproic acid, may also be used.

The polyethers with at least 2, generally from 2 to 8 and, preferably, 2or 3, hydroxyl groups used according to the invention are known and maybe prepared, e.g., by the polymerization of epoxides, e.g., ethyleneoxide, propylene oxide, butylene oxide, tetrahydrofurane oxide, styreneoxide or epichlorohydrin, each with itself, e.g., in the presence ofBF₃, or by addition of these epoxides, optionally as mixtures orsuccessively, to starting components which contain reactive hydrogenatoms such as alcohols or amines, e.g., water, ethylene glycol;propylene-1,3- or -1,2-glycol; trimethylol propane;4,4-dihydroxydiphenylpropane; aniline, ammonia, ethanolamine orethylenediamaine; sucrose polyethers such as those described, e.g., inGerman Auslegeschrifren Nos. 1,176,358 and 1,064,938, may also be usedaccording to the invention. It is frequently preferred to use polyetherswhich contain, predominantly, primarily OH groups (up to 90% by weight,based on the total OH groups contained in the polyether). Polyethersmodified with vinyl polymers such as those wich may be obtained bypolymerizing styrene or acrylonitrites in the presence of polyethers,(U.S. Pat. Nos. 3,383,351; 3,304,273; 3,523,093 and 3,110,695; andGerman Pat. No. 1,152,536) and polybutadienes which contain OH groupsare also suitable.

By "polythioethers" are meant, in particular, the condensation productsof thiodiglycol with itself and/or with other glycols, dicarboxylicacids, formaldehyde, aminocarboxylic acids or amino alcohols. Theproducts obtained are polythio-mixed ethers or polythioether esteramides, depending on the cocomponent.

The polyacetals used may be, for example, the compounds which may beobtaind from glycols, 4,4'-dihydroxydiphenylmethylmethane, hexanedioland formaldehyde. Polyacetals suitable for the invention may also beprepared by the polymerization of cyclic acetals.

The polycarbonates with hydroxyl groups used may be of the kind, e.g.,which may be prepared by reaction diols, e.g., propane-1,3 diol;butane-1,4-diol; and/or hexane-1,6-diol or diethylene glycol,triethylene glycol or tetraethylene glycol, with diarylcarbonates, e.g.,diphenylcarbonates or phosgens.

The polyester amides and polyamides include, e.g., the predominantlylinear condensates obtained from polyvalent saturated and unsaturatedcarboxylic acids or their anhydrides, any polyvalent saturated andunsaturated amino alcohols, diamines, polyamines and mixtures thereof.

Polyhydroxyl compounds which contain urethane or urea groups, modifiedor unmodified natural polyols, e.g., castor oil, carbohydrates andstarches, may also be used. Additional products of alkylene oxides withphenol formaldehyde resins or with ureaformaldehyde resins are alsosuitable for the purpose of the invention.

Organic hydroxyl silicate compound as produced in U.S. Pat. No.4,139,549 may also be used in this invention.

Examples of these compounds which are to be used according to theinvention have been described in High Polymers, Volume XVI,"Polyurethanes, Chemistry and Technology," published by Saunders-FrischInterscience Publishers, New York, London, Volume I, 1962, pages 32 to42 and pages 44 to 54, and Volume II, 1964, pages 5 and 16 and pages 198and 199; and in Kunststoff-Handbuch, Volume VII, Vieweg-Hochtlen,Carl-Hanser-Verlag, Munich, 1966, on pages 45 to 71.

If the polyisocyanates or the prepolymer which contains NCO groups havea viscosity above 2000 cP at 25° C., it may be advantageous to reducethe viscosity thereof by mixing it with a low-viscosity organicpolyisocyanate and/or an inert blowing agent or solvent.

Inorganic polyisocyanates and isocyanate-terminated polyurethanesilicate prepolymers may also be used in this invention.

Polyisocyanate curing agents and/or polyisocyanate activators(catalysts) may be used in the process of producing polyurethaneresinous or foamed products. The following are examples ofpolyisocyanate curing agents and activators:

1. Water.

2. Water containing 10% to 70% by weight of an alkali metal silicate,such as sodium and/or potassium silicate. Crude commercial alkali metalsilicate may contain other substances, e.g., calcium silicate, magnesiumsilicate, borates or aluminates and may also be used. The molar ratio ofalkali metal oxide to SiO₂ is not critical and may vary within the usuallimits, but is preferably between 4 to 1 and 0.2 to 1.

3. Water containing 20% to 50% by weight of ammonium silicate.

4. Water containing 5% to 40% by weight of magnesium oxide in the formof a colloidal dispersion.

5. Alkali metal metasilicate such as sodium metasilicate, potassiummetasilicate and commercial dry granular sodium and potassium silicates.Heating is required to start the curing reaction.

6. Water containing 20% to 70% by weight of silica sol.

7. Activators (catalysts) which act as curing agents and are added tothe polyurethane silicate prepolymer in the amount of 0.001% to 10% byweight. They may be added in water.

(a) Tertiary amines, e.g., triethylamine; tributylamine;N-methyl-morpholine; N,N,N',N'-tetramethylenediamine;1,4-diazobicyclo-(2,2,2)-octane; N-methyl-N'-dimethylaminoethylpiperazine; N,N-dimethylbenzylamine; bis(N,N-diethylaminoethyl)-adipate; N,N-diethylbenzylamine;pentamethyldiethylenetriamine; N,N-dimethylcyclohexylamine;N,N,N',N'-tetramethyl-1,3-butanediamine;N,N-dimethyl-beta-phenylethylamine; and 1,2-dimethylimidazole. Suitabletertiary amine activators which contain hydrogen atoms which arereactive with isocyanate groups include, e.g., triethanolamine;triisopanolamine; N,N-dimethylethanolamine; N-methyldiethanolamine;N-ethyldiethanolamine; and their reactive products with alkylene oxides,e.g., propylene oxide and/or ethylene oxide and mixtures thereof.

(b) Organo-metallic compounds, preferably organo-tin compounds such astin salts of carboxylic acid, e.g., tin acetate, tin octoate, tin ethylhexoate, and tin laurate and the dialkyl tin salts of carboxylic acids,e.g., dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleateor diocyl tin diacetate.

(c) Silaamines with carbon-silicon bonds are described, e.g., in BritishPat. No. 1,090,589, may also be used as activators, e.g.,2,2,4-trimethyl-1,2-silamorpholine or1,3-diethylaminoethyl-tetramethyldisiloxane.

(d) Other examples of catalysts which may be used according to theinvention, and details of their action are described inKunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen,Carl-Hanser-Verlag, Munich, 1966, on pages 96 and 102.

8. Water containing 1% to 10% by weight of bases which contain nitrogensuch as tetraalkyl ammonium hydroxides.

9. Water containing 1% to 10% by weight of alkali metal hydroxides suchas sodium hydroxide; alkali metal phenolates such as sodium phenolate oralkali metal alcoholates such as sodium methylate.

10. Water containing sodium polysulfide in the amount of 1% to 10% byweight.

11. Water containing 20% to 70% by weight of a water-binding agent,being capable of absorbing water to form a solid or a gel, such ashydraulic cement, synthetic anhydrite, gypsum or burnt lime.

12. Mixtures of the above-named curing agents.

Surface-active additives (emulsifiers and foam stabilizers) may also beused according to the invention. Suitable emulsifiers are, e.g., thesodium salts of ricinoleic sulphonates or of fatty acids, or salts offatty acids with amines, e.g., oleic acid diethylamin or stearic aciddiethanolamine. Other surface-active additives are alkali metal orammonium salts of sulphonic acids, e.g., dodecylbenzine sulphonic acidor dinaphthymethane disulphonic acid; or of fatty acids, e.g.,ricinoleic acid, or of polymeric fatty acids. The emulsifiers may beadded in an amount by weight up to 20%.

The foam stabilizers used are mainly water-soluble polyester siloxanes.These compounds generally have a polydimethylsiloxane group attached toa copolymer of ethylene oxide and propylene oxide. Foam stabilizers ofthis kind have been described in U.S. Pat. No. 3,629,308. Theseadditives are preferably used in quantities of 0% to 20%, but,preferably, 0.01% to 20%, by weight, based on the reaction mixture.

Negative catalyst, for example, substances which are acidic in reaction,e.g., hydrochloric acid or organic acid halides, known cell regulators,e.g., paraffins, fatty alcohols or dimethyl polysiloxanes, pigments ordyes, known flame-retarding agents, e.g., tris-chloroethylphosphate orammonium phosphate and polyphosphates, stabilizers against aging andweathering, plasticizers, fungicidal and bacteriocidal substances andfillers, e.g., barium sulphate, kieselguhr, carbon black or whiting, mayalso be used according to the invention.

Further examples of surface additives, foam stabilizers, cellregulators, negative catalysts, stabilizers, flame-retarding substances,plasticizers, dyes, fillers and fungicidal and bacteriocidal substancesand details about methods of using these additives and their action maybe found in Kunststoff-Handbuch, Volume VI, published by Vieweg andHochtlen, Carl-Hanser-Verlag, Munich, 1966, on pages 103 to 113. Thehalogenated paraffins and inorganic salts of phosphoric acid are thepreferred fire-retarding agents.

The preferred curing agent is an aqueous solution of silicates, sodiumsilicate and/or potassium silicate in water which is normally known aswater glass. Aqueous solutions of silicates may be prepared in the formof 25% to 54% silicates. Silicon sols which may have an alkaline or acidpH may also be used; they should have solid contents of 15% to 50%.Silica sols are generally used in combination with aqueous silicatesolutions. The choice of concentration depends mainly on the desired endproduct. Compact materials or materials with closed cells are,preferably, produced with concentrated silicated solutions which, ifnecessary, are adjusted to a lower viscosity by addition of alkali metalhydroxide. Solutions with concentrations of 40% to 70% by weight can beprepared in this way. On the other hand, to produce open-celled,light-weight foams, it is preferred to use silicate solutions withconcentrations of 20% to 45% by weight in order to obtain lowviscosities, sufficiently long reaction times and low unit weights.Silicate solutions with concentrations of 15% to 45% are also preferredwhen substantial quantities of finely divided inorganic fillers areused.

Suitable flame-resistant compounds may be used in the products of thisinvention such as those which contain halogen or phosphorus, e.g.,tributylphosphate, tris(2,3-dichloropropyl)-phosphate;polyoxypropylenechloromethylphosphonate; cresyldiphenylphosphate;tricresylphosphate; tris(betachloroethyl)-phosphate;tris-(2,3dichloropropyl)-phosphate; triphenylphosphate; ammoniumphosphate; perchlorinated diphenyl phosphate; perchlorinated terephenylphosphate; hexabromocyclodecane; tribromophenol; dibromopropylidiene,hexabromobenzene; octabromodiphenylether; pentabromotoluol;polytribromostyrol, tris-(bromocresyl)-phosphate; tetrabromobisphenol A;tetrabromophthalic acid anhydride; octabromodiphenyl phosphate;tri-(dibromopropyl)-phosphate; calcium hydrogen phosphate; sodium orpotassium dihydrogen phosphate; disodium or dipotassiumhydrogenphosphate; ammonium chloride, phosphoric acid; polyvinylchloridetetomers chloroparaffins as well as further phosphorus- and/orhalogen-containing flame-resistant compounds as they are described inKunststoff-Handbuch, Volume VII, Munich, 1966, pages 110 and 111, whichare incorporated herein by reference. The organic halogen-containingcomponents are, however, preferred in the polyurethane products.

The ratios of the essential reactants and optional reactants which leadto the polyurethane silicate resinous or foamed product of thisinvention may vary, broadly speaking, with ranges as follows:

(a) 1 to 95 parts by weight of an organic broken-down lignin-cellulosepolymer;

(b) 50 parts by weight of polyisocyanate, polyisocyanate orisocyanate-terminated polyurethane prepolymers;

(c) up to 20% by weight of a foam stabilizer;

(d) up to 50% by weight of a chemically inert blocking agent, boilingwithin the range of from -25° C. to 80° C.;

(e) up to 10% by weight of an activator;

(f) up to 200 parts by weight of a water-binding agent;

(g) 1 to 95 parts by weight of a polyol;

(h) up to 20% by weight of an emulsifier.

Percentages are based on the weight of the reactants, resinous product,polyol and polyisocyanate.

In the cases where the viscosity of the polyisocyanate is too high, itmay be reduced by adding a low-viscosity isocyanate, or even by addinginert solvents such as acetone, diethyl ether or diethylene glycol,ethyl acetate and the like.

In cases where the curing agent contains an aqueous alkali silicate, theisocyanate-terminated polyurethane prepolymer may be sulphonated. It isusually sufficient to react the isocyanate-terminated polyurethaneprepolymer with concentrated sulphuric acid or oleum of sulfur trioxidein order to produce a sulphonated poly(urethane silicate) prepolymercontaining the sulphonic group in the amount of 3-100milli-equivalents/100 g. The reaction will take place by thoroughlymixing the sulphuric acid or oleum or sulfur trioxide with theisocyanate-terminated polyurethane prepolymer at ambient temperature andpressure. In some cases where sulfur trioxide is used, an increasedpressure is advantageous. The polyisocyanate may be modified to containionic groups before reacting with the polyester-silicate resinousproducts.

The sulphonated isocyanate-terminated polyurethane prepolymer can bedirectly mixed with an aqueous silicate solution, in which case thecorresponding metal salt is formed in situ. The sulphonatedpoly(urethane silicate) prepolymer may be completely or partlyneutralized at the onset by the addition of amines, metal alcoholates,metal oxides, metal hydroxide or metal carbonates.

Water-binding components may be used in this invention, includingorganic or inorganic water-binding substances which have, first, theability to chemically combine, preferably irreversibly, with water and,second, the ability to reinforce the poly(urethane silicate) plastics ofthe invention. The term "water-binding component" is used herein toidentify a material, preferably granular or particulate, which issufficiently anhydrous to be capable of absorbing water to form a solidor gel such as mortar of hydraulic cement.

A water-binding component such as hydraulic cement, syntheticanhydrides, gypsum or burnt lime may be added to any of the componentsto produce a tough, somewhat flexible solid or cellular solid concrete.The water-binding component may be added in amounts from up to 200% byweight, based on the weight of the reactants. When a water-binding agentis added and when the curing agent is an aqueous alkali metal silicatesolution, a halogen or phosphorous-containing compound or mixturethereof may be added in the amount of 1% to 30% by weight, based on theweight of the reactants.

Suitable hydraulic cements are, in particular, Portland cement,quick-setting cement, blast-furnace Portland cement, mild-burnt cement,sulphate-resistant cement, brick cement, natural cement, lime cement,gypsum cement, pozzolan cement and calcium sulphate cement. In general,any mixture of fine ground lime, alumina and silica that will set to ahard product by admixture of water, which combines chemically with theother ingredients to form a hydrate, may be used. There are many kindsof cement which can be used in the production of the compositions of theinvention and they are so well known that a detailed description ofcement will not be given here; however, one can find such a detaileddescription in Encyclopedia of Chemical Technology, Volume 4, SecondEdition, published by Kirk-Othmer, pages 684 to 710, of the type ofcement which may be used in the production of this invention and whichare incorporated herein by reference.

Blowing agents may be used to improve or increase the foaming to producecellular solid plastics such as acetone, ethyl acetate, methanol,ethanol, halogenated alkaned, e.g., methylene chloride, chloroform,ethylidene chloride, vinylidene chloride, monofluorotrichloromethane,chlorodifuloromethane, butane, hexane of diethyl ether. Compounds whichdecompose at temperatures above room temperature with liberation ofgases, e.g., nitrogen, such as azo compounds, azoisobutyric acidnitrile, may also act as blowing agents. Compressed air may act as ablowing agent. Other examples of blowing agents and details of the useof blowing agents are described in Kunststoff-Handbuch, Volume VII,published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich, 1966,e.g., on pages 108 and 109, 453 to 455 and 507 to 510.

The proportions of the components may be adjusted to a highly cellularsolid. When water is used, it reacts with the NCO group to produce CO₂and pores are produced in the product by the evolved CO₂. In certaincases, the CO₂ is rapidly evolved and escapes before the producthardens, and a solid product can be produced, nearly completely free ofair cells. When a high silicate content, from 80% to 99% by weight ofdesireable, such as when the final product is required to have mainlythe properties of an inorganic silicate plastic, in particular,high-temperature resistance and complete flame resistance, an alkalimetal silicate may be added with copolymer or polyol or be reacted withthe polyisocyanate to produce a polyurethane prepolymer. In that case,the function of the polyisocyanate is that of a non-volatile hardenerwhose reaction product is a high-molecular-weight polymer which reducesthe brittleness of the product.

When an alkali catalyst or alkali metal silicate is used in theinvention, fine metal powders, e.g., powdered calcium, magnesium,aluminum or zinc, may also act as the blowing agents by bringing aboutthe evolution of hydrogen. Compressed ar may be mixed in the componentsand may also be used to mix the components, then be used as the blowingagent. These metal powders also have a hardening and reinforcing effect.

The properties of the foams (cellular solid) obtained from any givenformulation, e.g., their density in the moist state, depends to someextent on the details of the mixing process, e.g., the form and speed ofthe stirrer and the form of the mixing chamber, and also the selectedtemperature at which foaming is started. The foams will usually expand 3to 12 times their original volume.

The polyurethane silicate plastics produced by the invention have manyuses. The reaction mixture, with or without a blowing agent, may bemixed in a mixing apparatus; then the reaction mixture may be sprayed bymeans of compressed air or by the airless spraying process ontosurfaces; subsequently, the mixture expands and hardens in the form of acellular solid which is useful for insulation, filling, andmoisture-proofing coating. The foaming material may also be forced,poured or injection-molded into cold or heated molds, which may berelief molds or solid or hollow molds, optionally by centrifugalcasting, and left to harden at room temperature or at temperature up to200° C., at ambient pressure or at elevated pressure. In certain cases,it may be necessary to heat the mixing or spraying apparatus to initiatefoaming; then, once foaming has started, the heat evolved by thereaction between components continues the foaming until the reaction iscomplete. A temperature between 40° C. and 150° C. may be required inorder to initiate foaming. The blowing agent is usually added to thepolyisocyanate.

Reinforcing elements may quite easily be incorporated into the reactionmixtures. The inorganic and/or organic reinforcing elements may be,e.g., fibers, metal wires, foams, fabrics, fleeces or skeletons. Thereinforcing elements may be mixed with the reaction mixtures, forexample, by the fibrous web impregnation or by processes in which thereaction mixtures and reinforcing fibers are together applied to themold, for example, by means of a spray apparatus. The shaped productsobtainable in this way may be used as building elements, e.g., in theform of sandwich elements, either as such or after they have beenlaminated with metal, glass or plastics; if desired, these sandwichelements may be foamed. The products may be used as hollow bodies, e.g.,as containers for goods which may be required to be kept moist or cool,as filter materials or exchanges, as catalyst carriers or carriers ofother active substances, as decorative elements, furniture componentsand fillings or for cavities. They may be used in the field of modelbuilding and mold building, and the production of molds for metalcasting may also be considered.

Instead of blowing agents, finely divided inorganic or organic hollowparticles, e.g., hollow expanded beads of glass, plastics and straw, maybe used for producing cellular solid products. These products may may beused as insulating materials, cavity fillings, packaging materials,building materials which have good solvent resistance and advantageousfire-resistant characteristics. They may also be used as lightweightbuilding bricks in the form of sandwiches, e.g., with metal-coveringlayers for house building and the construction of motor vehicles andaircraft.

Organic or inorganic particles which are capable of foaming up or havealready been foamed may be incorporated in the fluid foaming reactionmixture, e.g., expanded clay, expanded glass, wood, cork, popcorn,hollow plastic beads such as beads of vinyl chloride polymers,polyethylene, styrene polymers, or foam particles of these polymers orother polymers, e.g., polysulphone, polyepoxide, polyurethane,poly(urethane silicate) copolymers, urea-formaldehyde,phenol-formaldehyde or polyimide polymers, or, alternatively, heaps ofthese particles may be permeated with foaming reaction mixture toproduce insulation materials which have good fire-resistancecharacteristics.

The cellular solid products of the invention, in the aqueous or dry orimpregnated state, may subsequently be lacquered metallized, coated,laminated, galvanized, vapor-treated, bonded or blocked. The cellularsolid products may be sawed, drilled, planed, polished, or other workingprocesses may be used to produce shaped products. The shaped products,with or without a filler, may be further modified in their properties bysubsequent heat treatment, oxidation processes, hot pressing, sinteringprocesses or surface melting or other compacting processes.

The novel cellular solid products of the invention are also suitable foruse as constructional materials due to their toughness and stiffness,yet they are still elastic. They are resistant to tension andcompression and have a high-dimensional stability to heat and high flameresistance. They have excellent sound-absorption capacity,heat-insulating capacity, fire resistance, and heat resistance whichmakes them useful for insulation. The cellular products of thisinvention may be foamed on the building site and, in many cases, used inplace of wood or hard fiber boards. Any hollow forms may be used forfoaming. The brittle foams may be crushed and used as a filler, as asoil conditioner, as a substrate for the propagation of seedlings,cuttings and plants or cut flowers.

The foamed or solid concrete produced by reaction of the organicbroken-down lignin cellulose polymer, polyol and polyisocyanate with awater-binding component may be used as surface coatings having goodadhesion and resistance-to-abrasion properties, as mortars, and formaking moled products, particularly in construction engineering andcivil engineering such as for building walls, igloos, boats and forroadbuilding, etc. These products are lightweight, thermal-insulatingmaterials with excellent mechanical properties and fire resistance. Theamount of water-binding component used varies greatly, depending on thetype of product desired, up to 200% by weight, based on the reactants.In certain cases, it is desirable to add sand and gravel in the amountof 1 to 6 parts by weight to each part by weight of the hydrauliccement. The mixture may be poured in place, trowled on or sprayed ontothe desired surface to produce a solid or cellular solid product.

Fillers in the form of powders, granules, wire, fibers, dumb-bell shapedparticles, crystallites, spirals, rods, beads, hollow beads, foamparticles, non-woven webs, pieces of woven or knitted fabrics, tapes andpieces of foil of solid inorganic or organic substances, e.g., dolomite,chalk, alumina, asbestos, basic silicic acids, sand, talc, iron oxides,aluminum oxide and hydroxides, alkali metal silicates, zeolites, mixedsilicates, calcium silicate, calcium sulphates, aliminosilicates,cement, basalt wool or powders, glass fibers, carbon fibers, graphite,carbon black, Al-; Fe-, Cri- and Ag-powders, molybdenum sulphide, steelwood, bronze or copper meshes, silicon powder, expanded clay particles,hollow glass beads, glass powder, lava and pumice particles, wood chips,woodmeal, cork, cotton, straw, popcorn, coke or particles of filled orunfilled, foamed or unfoamed, stretched or unstretched organic polymers,may be added to the mixture of the Components a, b and c in manyapplications. Among the numerous organic polymers which may be used,e.g., as powders, granules, foam particles, beads, hollow beads,foamable (but not-yet foamed) particles, fibers, tapes, woven fabrics,or fleeces, the following may be mentioned as examples: polystyrene,polyethylene, polypropylene, polyacrylonitrile, polybutadiene,polyisopropene, polytetrafluorethylene, aliphatic and aromaticpolyesters, melamine, urea, phenol resins, phenol silicate resins,polyacetal resins, polyepoxides, polyhydantoins, polyureas, polyethers,polyurethanes, polyimides, polyamides, polysulphones, polysulphones,polycarbonates and copolymers thereof.

The composite materials, according to the invention, may be mixed withconsiderable quantities of fillers without losing their advantageousproperties, and, in particular, composite materials which consistpredominantly of organic constituents which are preferably filled withinorganic fillers; where silicate constituents predominate, it ispreferably filled with organic fillers. Fillers which are particularlypreferred are chalk, talc, dolomite, gypsum, clay, anhydrite, glass,carbon and the conventional plastics and rubber waste.

In the production of surface coatings, bonds, putties or interlayers,particularly in the case of porous materials, it is preferred to usepolyisocyanates which have only a low isocyanate content, e.g., lessthan 5%, or prepolymers which are free from isocyanate groups. Themixture obtained in this way have a long pot life and may be applied inthin layers which gradually harden in the course of time. The liberatedCO₂ acts as the curing agent. In a two-stage or multistage hardening inwhich, for example, an excess of water is used, there is a rapidevolution of CO₂ and the polyurethane silicon acid resinous product isconverted into a workable form which may be used as putties, coatingagents, grouting materials or mortar. This thermoplastic form may alsobe injection-molded, extruded or worked up in a kneader.

In many cases, the polyurethane resinous and foamed products produced bythe invention are soluble in organic solvents and may be used as a toughcoating agent for wood and metal. The mixtures of the invention are alsosuitable for use as impregnating agents for finishing fibers. Themixtures may also be extruded through dies or slots and be convertedinto fibers and foils. These fibers and foils may be used for producingsynthetic incombustible paper or fleeces.

When the broken-down organic lignin-cellulose silicate polymer andpolyisocyanate are combined with expanded clay and an alkali metalsilicate solution, a very good concrete is obtained which can, forexample, be used as panels in the construction field. In this case, thefoam material (expanded clay) plays the part of the binding material.

DESCRIPTION OF PREFERRED EMBODIMENTS

My invention will be illustrated in greater detail by the specificexamples which follow, it being understood that these preferredembodiments are illustrative of, but not limited to, procedures whichmay be used in the production of broken-down organic lignin-cellulosesilicate polymers. Parts and percentages are by weight unless otherwiseindicated.

EXAMPLE 1

About 2 parts by weight of fir sawdust and 1 part by weight of hydratedsilica and mixed then placed on top of 3 parts by weight of sodiumhydroxide flakes, then heated to 150° C. to 220° C. then agitated atambient pressure for 5 to 60 minutes or until the mixture softens andexpands into a brown, thick liquid which solidifies on cooling, therebyproducing an organic broken-down sodium lignin-cellulose silicateproduct.

Water is added to the broken-down sodium lignin-cellulose silicatepolymer to produce a 30% aqueous solution which is filtered to removeany unreacted cellulose and hydrated silica, ethyl chloride gas isslowly added to the solution in an autoclave under 500 to 1500 psi inamount wherein the sodium atoms about equal the chloride atoms, whilevigorously agitating the mixture for about 30 minutes at a temperatureof 150° C. to 200° C. The reaction is complete in 30 minutes to 8 hours,thereby producing a light-brown broken-down ethyl lignin-cellulosesilicate polymer which settles out. The water, salt and unreactedcomponents are removed by filtration.

EXAMPLE 2

About 2 parts by weight of small plant particles listed below and 1.5parts by weight of fine granular hydrated silica are mixed, then placedon top of 3 parts by weight of sodium hydroxide, then heated to 150° C.to 220° C., then agitated at ambient pressure, with care being taken toavoid burning the mixture, for 5 to 60 minutes; the mixture begins toexpand and a brown, thick liquid broken-down sodium cellulose silicatepolymer. The liquid solidifies on cooling and is ground into a powder.The powder is soluble in water, alcohols, polyhydric organic compoundsand other solvents.

(a) oak sawdust

(b) fir sawdust

(c) ash sawdust

(d) seaweed

(e) cotton

(f) Corn cobs

(g) cotton stalks

(h) bagasse

(i) paper

(j) oat straw

Water is added to the broken-down sodium lignin-cellulose polymerproduced from oak sawdust filtered to remove any unreacted sawdust, anda 70% aqueous solution of the broken-down sodium cellulose silicatepolymer is produced; then propyl chloride is slowly added to thereaction in an autoclave in an amount wherein the chloride atoms areabout equal to the sodium atoms, while vigorously agitating the mixtureat a pressure of 500 to 1500 psi and temperature of 150° C. to 200° C.for about 30 minutes. The reaction is complete in 30 minutes to 8 hours,thereby producing a light-brown propyl lignin-cellulose silicate polymerwhich precipitates out. The water, salt and unreacted components areremoved by filtration and may be further treated to recover thecarbohydrates.

EXAMPLE 3

Methyl chloride is slowly added to an aqueous solution containing 60%broken-down sodium lignin-cellulose silicate polymer as produced inExample 2c and 2% sodium lignin sulfonate in an autoclave at 1000 to1500 psi while agitating and keeping the temperature between 150° C. to200° C. for 30 minutes. The reaction is complete in 30 minutes to 8hours, thereby producing a methyl lignin-cellulose silicate polymer. Themethyl chloride is added in an amount wherein the chloride atoms areabout equal to the sodium atoms.

EXAMPLE 4

The brokwn-down alkali lignin-cellulose silicate polymer produced inExample 2f is mixed with ethyl acetate in an about equal amount whileagitating for about 30 minutes, thereby producing a broken-down organiclignin-cellulose silicate polymer. The polymer is recovered byfiltration.

EXAMPLE 5

Propane -1-dihydrogen phosphate is slowly added to a broken-down alkalimetal cellulose silicate polymer as produced in Example 2h in an amountwherein the phosphate radicals are about equivalent to the sodiumradicals while agitating at a temperature just below the boilingtemperature of the reactants for 30 minutes. The reaction is complete in30 minutes to 8 hours, thereby producing a propyl lignin-cellulosesilicate polymer.

EXAMPLE 6

About 3 parts by weight of a broken-down alkali metal lignin-cellulosesilicate polymer, as produced in Example 2f are ground into a finepowder, then bis-monochloroacetic acid, in the amount wherein thechloride atoms are about equal to the sodium atoms in the mixture, isslowly added while agitating at a temperature just below the boilingtemperature of monochloroacetic acid for about 30 minutes. The reactionis complete in 30 minutes to 8 hours, thereby producing a carboxymethyllignin-cellulose silicate polymer.

EXAMPLE 7

An amount of nitrobenzene, wherein the nitro and alkali metal radicalsare about equal is slowly added to the broken-down alkali metalcellulose silicate polymer produced in 2b while agitating at atemperature just below the boiling temperature of paranitrobenzene forabout 30 minutes. The reaction is complete in 30 minutes to 8 hours,thereby producing a benzyl lignin-cellulose silicate polymer.

EXAMPLE 8

About 10 parts by weight of broken-down alkali metal lignin-cellulosesilicate polymers as produced in Example 2j are dissolved in ethanol,then butane-1-hydrogen sulfate is slowly added, in an amount wherein thehydrogen sulfate radicals are about equal to the sodium radicals, whileagitating for about 30 minutes. The reaction is complete in 30 minutesto 8 hours, thereby producing a brown organic lignin-cellulose silicatepolymer.

Other substituted organic compounds may be used in place ofbutane-1-hydrogen sulfate such as para chlorobenzene; 2-nitrotoluene;1-chloro-2-propanol; methyl sulfate; 1,1-bromopropane; ethyl sulfate;1-bromo-2-butene; ethylene chlorohydrin; ethyl hydrogen sulfate;dichloroacetic acid; p-chlorobenzyl and mixtures thereof.

EXAMPLE 9

About 10 parts by weight of the broken-down sodium lignin-cellulosesilicate polymer as produced in 2b and 10 parts by weight ofpolyethylene glycol (mol. wt. 380 to 420) are mixed and heated until thepolymer goes into solution; then ethyl chloride is slowly added in anautoclave at 1000 to 1500 psi in an amount wherein the chlorine atomsabout equal the sodium atoms while agitating at a temperature between150° C. to 200° C. for about 30 minutes, thereby producing an ethyllignin-cellulose silicate polymer.

About 10 parts by weight of TDI and 0.05 part by weight oftriethylenediamine are added to the ethyl lignin-cellulose silicatepolymer in the polyethylene glycol and thoroughly mixed at ambienttemperature. The mixture begins to expand in a few seconds and expands 8to 12 times its original volume to produce a rigid polyurethane silicatefoam which is light brown in color, tough and somewhat flexible.

Other polyols and polyisocyanate may be used in this example in place ofpolyethylene glycol and TDI. The polyurethane silicate foam may beproduced in large slabs, then cut into sheets of the desired thicknessand use as sound and thermal insulation in homes, buildings, aircraftand automobiles.

EXAMPLE 10

Ethyl acetate is slowly added in an amount when in 1 mol of the ethylacetate is added per 1 mol of the sodium hydroxide present in thebroken-down sodium lignin-cellulose silicate polymer produced in 2bwhile agitating at a temperature just below the boiling point of theethyl acetate for about 30 minutes, thereby producing brown granules ofa broken-down organic lignin-cellulose silicate polymer.

The polymer is then washed with water filtered to remove the salt, thendried. The dried polymer is then heated to 160° C. to 200° C., thenforced into a mold under pressure to produce a useful object such asknobs, handles, art objects, etc., which are brown in color and arerigid and tough.

EXAMPLE 11

About 10 parts of the broken-down organic lignin-cellulose silicatepolymer as produced in Example 10 is mixed with 10 parts by weight ofpolyethylene glycol (mol. wt. 380 to 420) and the polymer goes intosolution, then 15 parts by weight of TDI are added and thoroughly mixed.About 0.3 part by weight of TDI are added and thoroughly mixed. About0.3 part by weight of triethylenediamine is added and thoroughly mixed.The mixture expands 8 to 12 times its original volume, thereby producinga rigid, cream-colored polyurethane silicate foam.

EXAMPLE 12

About 10 parts by weight of broken-down alkali metal lignin-cellulosesilicate polymer as produced in Example 1 and 5 parts by weight of anaqueous solution containing 37% by weight of formaldehyde are mixed,then heated to below the boiling point of the reactants while agitatingfor 10 to 120 minutes, thereby producing an aldehyde-broken-down alkalimetal lignin-cellulose silicate polymer; then propane-1-hydrogen sulfateis added to the aqueous solution of aldehyde-broken-down alkali metallignin-cellulose silicate polymer in an amount wherein the hydrogensulfate radicals are about equal to the alkali metal radicals, whileagitating at ambient temperature and pressure for about 30 minutes. Thereaction is complete in 30 minutes to 8 hours, thereby producing analdehyde broken-down lignin-cellulose propionate silicate polymer.

Other aldehydes may be used in place of formaldehyde such asacetaldehyde, propionic aldehyde, furfural, crotonaldehyde, acrolein,benzaldehyde, butyl aldehyde, pentanals, hexanals, heptanals, octanalsand mixtures thereof.

Other substituted organic compounds listed in the specification may beused in place of propane hydrogen sulfate.

EXAMPLE 13

The dried powdered broken-down organic lignin-cellulose silicate polymeras produced in Example 10 is mixed with about equal parts by weight of"MDI" and 0.2% by weight of trimethylamine, based on the reactantspolymer. The mixture expands in a few seconds to produce a rigidpolyurethane silicate foam.

EXAMPLE 14

About 20 parts by weight of the broken-down lignin-cellulose propionatesilicate polymer as produced in Example 11 and 20 parts by weight ofisocyanate-terminated polyurethane prepolymer listed below and 2 partsby weight of water containing 10% by weight of triethyleneamine and 30%by weight of sodium silicate are mixed and in a few minutes, a solidpolyurethane silicate resinous product is produced. This resinousproduct may be used as a cavity filler.

    __________________________________________________________________________    Example                                                                            Isocyanate-terminated Polyurethane Prepolymer                            __________________________________________________________________________    a    polyphenyl-polymethane-isocyanate with polyethylene oxide mono-               hydric alcohol (mol. wt. 1100), initiated on trimethylol propane              to produce a prepolymer with an NCO content of about 18%.                b    TDI (tolylene diisocyanate) with polyethylene (mol. wt. 1000)                 to produce a prepolymer with an NCO content of about 24%.                c    Residue of tolylene diisocyanate distillation with about 20% by               weight of NCO with polyethylene glycol (mol. wt. 1500) to pro-                duce a prepolymer with an NCO content of about 10%.                      d    Tolylene diisocyanate with castor oil to produce a prepolymer with            an NCO content of about 15%.                                             e    Tolylene diisocyanate with a liquid hydroxyl-terminated poly-                 butadiene (mol. wt. 500) to produce a prepolymer with an NCO                  content of about 7%.                                                     f    Toluene diisocyanate with a hydroxyl-group-containing polysulfide             polymer to produce a prepolymer an NCO content of about 12%.             g    Methylene bis-phenyl diisocyanate with a liquid polyepichloro-                hydrin to produce a prepolymer of about 16%.                             h    Tolylene diisocyanate with a polyester (4 mols of glycerol, 2.5               mols of adipic acid and 0.5 mol of phthalic anhydride) to pro-                duce a prepolymer with an NCO content of about 20%.                      __________________________________________________________________________

EXAMPLE 15

About 10 parts by weight of the aldehyde broken-down lignin-cellulosepropionate silicate polymer as produced in Example 12, 10 parts byweight of a sucrose amine polymer (POLY G 71-356 as produced by OlinChemical), 15 parts by weight of MDI and 10 parts by weight of sodiummetal silicate pentahydrate are mixed at 30° C. to 40° C. The mixturebegins to expand in 15 to 45 seconds and expands 8 to 12 times itsoriginal volume to produce a rigid tough polyurethane silicate foam. Thefoam is flame-resistant and may be used in construction of doors, panelsand be used as thermal and sound insulation. It may be cut into thedesired width and thickness. Other alkali metal silicates may be used inplace of sodium silicate.

EXAMPLE 16

About 10 parts by weight of the dried broken-down ethyl lignin-cellulosepolymer as produced in Example 1, 10 parts by weight of polypropyleneglycol (mol. wt. 1200) 0.5 part by weight of triethylenediamine, 15parts by weight of MDI, 30 parts by weight of Portland Cement and 30parts by weight of plaster's sand are mixed thoroughly. The mixture isthen poured into 4"×6"×16" concrete block molds in the amount of 1/2" to3/4" in depth. In a few seconds to 1 minute, the mixture begins toexpand and fills the molds. The mixture hardens within 5 minutes and istaken from the mold and placed in water for about 2 minutes. The excesscement is cured with the water, thereby producing polyurethane silicateconcrete blocks. These blocks may be used for building walls which haveexcellent fire-resistance.

EXAMPLE 17

About 10 parts by weight of moist, broken-down alkali metallignin-cellulose silicate polymer as produced in Example 2b and 6 partsby weight of sodium chloroacetate are thoroughly mixed at ambienttemperature and pressure, then agitated for 30 minutes to 8 hours,thereby producing a sodium carboxymethyl lignin-cellulose silicatepolymer.

The sodium carboxymethyl lignin-cellulose silicate polymer is thentreated with a weak acid solution such as sodium bicarbonate or anacid-type cation exchange resin until neutralized, thereby producing acarboxymethyl lignin-cellulose silicate polymer.

EXAMPLE 18

Fine granular broken-down alkali metal lignin-cellulose silicate polymeras produced in Example 2b and chloroacetic acid in an amount wherein thealkali metal radicals are about equal to the chlorine atoms are mixedand agitated for about 30 minutes to 8 hours, thereby producingcarboxymethyl cellulose silicate polymer.

EXAMPLE 19

About 100 parts by weight of broken-down alkali metal lignin-cellulosesilicate polymer as produced in Example 2b in ethyl alcohol is added toa reactor (autoclave) and ethyl chloride gas is slowly added underpressure while agitating. The temperature is slowly raised to 180° C. to200° C. under a pressure of 1000 to 1500 psi until no furtherconsumption of ethyl chloride occurs. The ethyl lignin-cellulosesilicate polymer is separated from the salt by using a solvent such asacetone to extract the polymer. The polymer is then recovered byevaporating the solvent or precipitating it from the acetone.

EXAMPLE 20

About 100 parts by weight of moist broken-down alkali metallignin-cellulose silicate polymer as produced in Example 2b and 10 partsby weight of propylene oxide are added to an autoclave, then ethylchloride gas is slowly added to the autoclave in an amount wherein thealkali metal radicals are about equal to the chlorine atoms. Thetemperature is raised to 175° C. to 200° C. while agitating at apressure of 500 to 1500 psi for 30 minutes to 8 hours, thereby producinga hydropropyl ethyl lignin-cellulose silicate polymer. The salt is thenremoved by washing the polymer.

Other organic oxides may be used in place of propylene oxide, such asethylene oxide, styrene oxide, butylene oxide, tetrahydrofuran andmixtures thereof.

EXAMPLE 21

About 100 parts by weight of moist broken-down alkali metallignin-cellulose silicate polymer as produced in Example 2c and 10 partsby weight of propylene oxide are added to an autoclave, then methylchloride gas is added in an amount wherein the alkali metal radicals areabout equal to the chlorine atoms while agitating, then the temperatureis raised to 150° C. to 200° C. at a pressure of 500 to 1500 psi for 30minutes to 8 hours, thereby producing an hydropropyl methyllignin-cellulose silicate polymer.

EXAMPLE 22

About 100 parts by weight of moist broken-down alkali metallignin-cellulose silicate polymer as produced in 2f are added to anatuoclave, then methyl sulfate is added in an amount wherein the alkalimetal radicals are about one-half as many as the sulfate radicals, whileagitating at a temperature of 150° C. to 200° C. and up to 1500 psi for30 minutes to 8 hours, thereby producing a methyl lignin-cellulosesilicate polymer and salt.

EXAMPLE 23

About 100 parts by weight of the broken-down alkali metal cellulosesilicate polymer as produced in Example 2e and an equal amount ofchloroacetic acid and ethylene chlorohydrin, in an amount wherein thealkali metal radicals about equal the chlorine atoms, are mixed atambient temperature and pressure and are agitated for 30 minutes to 8hours, thereby producing a hydroxyl ethyl carboxymethyl cellulosesilicate polymer and salt.

EXAMPLE 24

About 100 parts by weight of the moist broken-down alkali metallignin-cellulose silicate polymer and about equal parts by weight ofchloroacetic acid and epichlorohydrin, in an amount wherein the alkalimetal radicals are about equal to the chlorine atoms, are mixed, thenagitated for 30 minutes to 8 hours at a temperature between ambient andthe boiling temperature of the reactants, thereby producing acarboxymethyl lignin-cellulose propyl epoxy silicate resin.

EXAMPLE 25

About 100 parts by weight of moist broken-down alkali metallignin-cellulose silicate polymer as produced in Example 2b andtrichlorobutylene oxide, in an amount wherein about one-third as manyalkali metal radicals as chlorine atoms are present, are mixed, thenagitated at a temperature below the boiling temperature of the reactantsfor 30 minutes to 8 hours, thereby producing an organic lignin cellulosesilicate polymer.

EXAMPLE 26

About 100 parts by weight of moist broken-down alkali metallignin-cellulose silicate polymer as produced in Example 2b and 50 partsby weight of acrylonitrile are mixed, then agitated at a temperature upto the boiling temperature of acrylonitrile and at ambient pressure for30 minutes to 8 hours, thereby producing a cyanoethylatedlignin-cellulose silicate polymer and salt. The salt is removed bywashing.

EXAMPLE 27

About 100 parts by weight of moist broken-down alkali metallignin-cellulose silicate polymer as produced in Example 2b and aboutequal parts by weight of benzyl chloride and vinylidene chloride, in anamount wherein the alkali metal radicals and chlorine atoms are aboutequal, are mixed in an autoclave, then agitated at a temperature justbelow the boiling point of the reactants for 30 minutes to 8 hours,thereby producing an ethylene benzyl lignin-cellulose silicate polymer.

EXAMPLE 28

About 100 parts by weight of broken-down alkali metal lignin-cellulosesilicate polymer as produced in Example 2b and vinyl acetate, in anamount wherein the alkali metal radicals are about equal to the acetateradicals, are mixed, then agitated for 30 minutes to 8 hours, therebyproducing an organic lignin-cellulose silicate polymer.

EXAMPLE 29

About 100 parts by weight of broken-down alkali metal lignin-cellulosesilicate polymer as produced in Example 2b and acetic anhydride, in anamount wherein the mols of alkali metal radical are about equal to themols of acetic anhydride, are mixed, then agitated at a temperature upto the boiling point of the reactants, thereby producing alignin-cellulose acetate silicate polymer and sodium acetate. The saltis removed by washing or by using a solvent.

EXAMPLE 30

About 100 parts by weight of broken-down alkali metal lignin-cellulosesilicate polymer produced in Example 2b and about equal parts by weightof acetic anhydride, propylene oxide and ethyl hydrogen sulfate, in anamount wherein the alkali metal radicals and the hydrogen sulfateradicals are about equal, are mixed, then agitated at a temperature upto the boiling temperature of the reacants for 30 minutes to 8 hours,thereby producing a hydroxypropyl ethyl lignin-cellulose acetatesilicate polymer and salt.

EXAMPLE 31

About 100 parts by weight of broken-down alkali metal lignin-cellulosesilicate polymer as produced in Example 2b and chloroacetic anhydride,in an amount wherein the alkali metal radical and chlorine atoms areabout equal, are mixed, then agitated at a temperature up to the boilingtemperature of the reactants and at ambient pressure for 30 minutes to 8hours, thereby producing a carboxymethyl lignin-cellulose acetatesilicate polymer and salt.

EXAMPLE 32

About equal parts by weight of an organic lignin-cellulose silicatepolymer as produced in the listed examples, polyethylene glycol (mol.wt. 600), containing 2% by weight of triethylenediamine, 10% by weightof trichlorotrifluoroethane and 2% sodium doctyl sulfosuccinate, and MDI(PAPI 27 produced up Upjohn) are mixed thoroughly. The mixture begins toexpand in 15 to 45 seconds, producing a rigid polyurethane foam.

    ______________________________________                                                                         Pro-                                                                          duced                                                                         in                                           Ex-                              Exam-                                        ample                                                                              Organic Lignin-Cellulose Polymer                                                                          ple                                          ______________________________________                                        a    Ethyl lignin-cellulose silicate polymer.                                                                  1                                            b    Propyl lignin-cellulose silicate polymer.                                                                 2                                            c    Methyl cellulose silicate polymer.                                                                        3                                            d    Ethyl lignin-cellulose silicate polymer.                                                                  4                                            e    Propyl lignin-cellulose silicate polymer.                                                                 5                                            f    Carboxymethyl lignin-cellulose silicate polymer                                                           6                                            g    Benzyl lignin-cellulose silicate polymer                                                                  7                                            h    Butyl lignin-cellulose silicate polymer                                                                   8                                            i    Ethyl lignin-cellulose silicate polymer                                                                   10                                           j    Formaldehyde propyl lignin-cellulose silicate                                 polymer.                    12                                           k    Carboxymethyl lignin-cellulose silicate polymer.                                                          17                                           l    Hydropropyl ethyl lignin-cellulose silicate polymer                                                       20                                           m    Hydropropyl methyl lignin-cellulose silicate                                  polymer.                    21                                           n    Hydroxy ethyl carboxymethyl cellulose silicate                                polymer.                    23                                           o    Carboxymethyl lignin-cellulose propyl epoxy sili-                             cate resin.                 24                                           p    Lignin-cellulose chlorobutylene epoxy silicate                                resin                       25                                           q    Ethylene lignin-cellulose silicate polymer.                                                               28                                           r    Lignin-cellulose acetate silicate polymer.                                                                29                                           s    Hydroxypropyl ethyl lignin-cellulose acetate                                  silicate polymer.           30                                           t    Carboxymethyl lignin-cellulose acetate silicate                               polymer.                    31                                           ______________________________________                                    

EXAMPLE 33

About 100 parts by weight of broken-down alkali lignin-cellulosesilicate polymer as produced in Example 2b, 100 parts by weight of a 37%aqueous solution of formaldehyde and ethylene hydrohydrin, in an amountwherein the alkali metal radicals are about equal to the chlorine atoms,are mixed, then agitated at a temperature up to the boiling point of thereactants for 30 minutes to 8 hours, thereby producing a formaldehydehydroxyethylene lignin-cellulose silicate resin and salt.

EXAMPLE 34

About 100 parts by weight of broken-down lignin-cellulose silicatepolymer as produced in Example 2b, 25 parts by weight of crotonaldehydeand allyl halide, in an amount wherein the chlorine atoms are aboutequal to the alkali metal radicals, are mixed at ambient temperature andpressure, then agitated at a temperature below the boiling temperatureof allyl chloride for 30 minutes to 8 hours, thereby producing analdehyde allyl lignin-cellulose silicate polymer and salt.

EXAMPLE 35

About 100 parts by weight of broken-down lignin-cellulose silicatepolymer as produced in Example 2b, about equal parts by weight of aceticanhydride and ethylene chlorohydrin in an amount wherein the alkalimetal radicals are about equal to the chlorene atoms and acetateradicals, plus 20 parts by weight of propylene oxide are mixed atambient temperature and pressure, then agitated for 30 minutes to 8hours, thereby producing an organic lignin-cellulose silicate polymer.

About 30 parts by weight of the organic lignin-cellulose silicatepolymer, 10 parts by weight of polyethylene glycol (380 mol. wt.)containing 1% by weight of triethylenediamine, parts by weight of MDI("PAPI" produced by Upjohn) and 6 parts by weight oftrichlorotrifluoroethane are mixed. In 15 to 45 seconds, the mixturebegins to expand and produces a rigid polyurethane foam which weighsabout 3 lbs. per cubic foot and is tan in color. The foam may be usedfor insulation, sound proofing, door cores, construction panels, artobjects, etc.

Although specific materials and conditions were set forth in the aboveexamples, these were merely illustrative of preferred embodiments of myinvention. Various other compositions, such as the typical materialslisted above, may be used, where suitable. The reactive mixtures andproducts of my invention may have other agents added thereto to enhanceor otherwise modify the reaction and products.

Other modifications of my invention will occur to those skilled in theart upon reading my disclosure. These are intended to be included withinthe scope of my invention, as defined in the appended claims.

I claim:
 1. The process for the production of a polyurethane silicate product by mixing and reacting a broken-down alkali metal lignin-cellulose silicate polymer and a substituted organic compound having a substituent which will split off during the reaction to said broken-down alkali metal lignin-cellulose silicate polymer in the amount wherein the mols of the substituted radicals are about equal to the mols of the alkali radicals in the mixture thereby producing a broken-down organic lignin-cellulose silicate polymer then 1 to 95 parts by weight of the broken-down organic lignin-cellulose silicate polymer and 50 parts by weight of a polyisocyanate or a polyisothiocyanate are mixed and reacted thereby producing a polyurethane silicate product.
 2. The process of claim 1 wherein the substituted organic compound contains at least one substituent, selected from the group consisting of acid sulfate, nitrate, sulfate, acid phosphate, bicarbonate, formate, acetate, propionate, laurate, oleate, stearate, oxalate, acid malonate and tartrate, acid citrate, halogens and mixtures thereof.
 3. The process of claim 1 wherein an emulsifying or dispersing agent selected from the group consisting of lignin sulfonate, alkyl aryl sulfonates, aryl alkyl sulfonates, sorbitan monolaurates, alkyl aryl sulfates, methyl cellulose, sulfonated petroleum fractions, polymerized aryl alkyl sulfonates, soybean lecithin, silicone surfactants and mixtures thereof in an aqueous solution is added to the unreacted mixture of broken-down lignin-cellulose polymer and substituted organic compound.
 4. The process of claim 1 wherein the substituted organic compound is an alkyl halide.
 5. The product produced by the process of claim
 1. 6. The process of claim 1 wherein the broken-down alkali metal lignin cellulose silicate polymer is first added to a solvent selected from the group consisting of water, methanol, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, glycerol, furfuryl alcohol, polyester polymer with 2 or more hydroxyl groups, surcose amine polymer with 2 or more hydroxyl groups, polyether polymers with 2 or more hydroxyl groups and mixtures thereof.
 7. The process of claim 1 wherein the broken-down alkali metal lignin-cellulose silicate polymer is first reacted with an aldehyde selected from the group consisting of formaldehyde, acetaldehyde, propionic aldehyde, furfural crotonaldehyde, acrolein, butyl aldehyde, paraformaldehyde, pentanals, hexanols, heptanals and mixtures thereof in the ratio of 1 to 5 parts by weight of the aldehyde to 2 parts by weight of the broken-down alkali metal lignin-cellulose silicate polymer.
 8. The product produced by the process of claim
 7. 9. The process of claim 1 wherein the polyisocyanate is selected from the group consisting of aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates and mixtures thereof.
 10. The process of claim 1 wherein the polyisocyanate is a phosgenation product of aniline condensation.
 11. The process of claim 1 wherein 1 to 95 parts by weight of a polyol is added with the polyisocyanate or polyisothiocyanate and is selected from the group consisting of polyether glycols, polyhydric alcohols, polyhydric alcohols, castor oil and polyesters, polyamides, polyacetals and polycarbonates which contain 2 or more hydroxyl groups per molecule and mixtures thereof.
 12. The product produced by the process of claim
 11. 13. The process of claim 1 wherein up to 200 parts by weight of a water-binding agent, percentages based on the weight of the reactants are added with the polyisocyanate and selected from the group consisting of hydraulic cement synthetic anhydride, gypsum and burnt lime.
 14. The product produced by the process of claim
 13. 15. The process of claim 1 wherein an isocyanate-terminated polyurethane prepolymer is used in place of the polyisocyanate and selected from the group consisting of an isocyanate-terminated polyether, isocyanate-terminated polybutadiene, isocyanate-terminated polysulfide and mixtures thereof.
 16. The product produced by the process of claim
 15. 17. The process of claim 1 wherein an additional step is taken wherein an organic compound is added with the broken-down alkali metal lignin-cellulose silicate polymer or substituted organic compound in an amount up to the amount by weight of the substituted organic compound, and selected from the group consisting of ethylene oxide, propylene oxide, styrene oxide, butylene oxide, tetrahydrofuran and mixtures thereof.
 18. The product produced by the process of claim
 17. 19. The process of claim 1 wherein an additional step is taken wherein an epihalohydrin selected from the group consisting of epichlorohydrin, epibromohydrin, methyl epichlorohydrin and mixtures thereof, is added with the substituted organic compound in an amount up to the amount by weight of the substituted organic compound.
 20. The product produced by the process of claim
 19. 